US5041586A - Method of preparing a silyphosphate mixture, silyphosphate mixture and its use in stabilizing metal silanolates in siloxane polymers - Google Patents
Method of preparing a silyphosphate mixture, silyphosphate mixture and its use in stabilizing metal silanolates in siloxane polymers Download PDFInfo
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- US5041586A US5041586A US07/622,051 US62205190A US5041586A US 5041586 A US5041586 A US 5041586A US 62205190 A US62205190 A US 62205190A US 5041586 A US5041586 A US 5041586A
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- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 37
- 229920000642 polymer Polymers 0.000 title description 17
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title description 8
- 229910052751 metal Inorganic materials 0.000 title description 3
- 239000002184 metal Substances 0.000 title description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 110
- YIKQLNRXIWIZFA-UHFFFAOYSA-N silyl dihydrogen phosphate Chemical compound OP(O)(=O)O[SiH3] YIKQLNRXIWIZFA-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 55
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- UQFOCNGSTJRLHY-UHFFFAOYSA-N trisilyl phosphate Chemical compound [SiH3]OP(=O)(O[SiH3])O[SiH3] UQFOCNGSTJRLHY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 43
- 229910021645 metal ion Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 150000007514 bases Chemical class 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000012808 vapor phase Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 12
- IALUUOKJPBOFJL-UHFFFAOYSA-N potassium oxidosilane Chemical compound [K+].[SiH3][O-] IALUUOKJPBOFJL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- -1 polydimethylsiloxane Polymers 0.000 description 53
- 239000003054 catalyst Substances 0.000 description 25
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 20
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 230000006641 stabilisation Effects 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 238000011067 equilibration Methods 0.000 description 7
- 229910001414 potassium ion Inorganic materials 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008707 rearrangement Effects 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019201 POBr3 Inorganic materials 0.000 description 2
- 229910019213 POCl3 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- TWHXWYVOWJCXSI-UHFFFAOYSA-N phosphoric acid;hydrate Chemical compound O.OP(O)(O)=O TWHXWYVOWJCXSI-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/095—Compounds containing the structure P(=O)-O-acyl, P(=O)-O-heteroatom, P(=O)-O-CN
Definitions
- This invention relates to a method of making silylphosphates, to the silylphosphates, and their use in stabilizing alkali metals and alkaline earth metals in polyorganosiloxanes.
- Polydiorganosiloxanes are used in many products, such as various kinds of silicone rubbers and fluids. Many of the products require property stability under high temperature exposure to function properly in their intended utility. Because the polydiorganosiloxanes are most often made by a polymerization process involving strong base equilibration of linear polydiorganosiloxane hydrolyzates or cyclic polydiorganosiloxanes and because this equilibration proceeds via a silicon-oxygen-silicon bond breakage and reformation, the basic polymerization catalyst used must be rendered ineffective if it remains in the final product. The amount of the basic compound is very small and difficult to remove at reasonable cost, so techniques have been developed to reduce the catalyst's harmful effects. The methods of neutralizing the catalyst's activity have varied effectiveness and each method seems to have one or more disadvantages.
- Polydiorganosiloxane can be prepared by the well known process of converting low molecular weight linear polydiorganosiloxanes and cyclic polydiorganosiloxanes by heating above 100° C. in the presence of potassium hydroxide or potassium silanolate.
- Other known alkali metal catalysts for this kind of polymerization are sodium hydroxide, cesium hydroxide, lithium hydroxide, and their corresponding silanolates or siloxanates.
- a ring opening reaction takes place with the formation of linear polymers.
- the resulting product of the equilibration reaction is about 85% linear polymer and 15% cyclic polydimethylsiloxanes.
- the presence of the cyclic siloxanes in products is undesirable because they are of low molecular weight and have a sufficiently high vapor pressure to cause problems during use, such as problems in closed or semiclosed conditions where electrical or electronic equipment is in close proximity with silicone rubber and therefore, these cyclic siloxanes should be removed.
- the inventors in this application use the term stabilizing the catalyst or stabilization of the catalyst to mean reducing the deleterious activity of metal ions resulting from polymerization reactions, thereby making them ineffective, for the most part, to cause Si-O-Si bond rearrangement and cyclic formation.
- One method of neutralizing the basic catalyst is the use of various types of acids.
- One difficulty with strong acids such as hydrochloric acid or sulfuric acid is that the amount of the acid used must be very carefully controlled because either excess base or excess acid will be detrimental to the final linear polydiorganosiloxanes stability.
- Both acids and bases are known equilibration catalysts, thus both produce similar results if left in the product. It is known that excess acid will cause degradation of the product similar to the degradation resulting from base such as alkali metal hydroxides. It is difficult to get the base completely neutral using a strong acid and would be very expensive and time consuming. Weak acids have also been used, such as acetic acid, but these acids have a similar problem.
- Phosphoric acid because it is a buffering kind of acid, has the ability to overcome the strong acid problem of neutralizing the basic catalysts used in the preparation of linear polydiorganosiloxane through an equilibration reaction.
- phosphoric acid is not soluble in the linear polydiorganosiloxane or in the cyclic polydiorganosiloxanes and to be an effective catalyst stabilizer it needs to be soluble so that it can get to the alkali metal ions which are often located, when equilibrium is reached, on the terminal silicon atoms of the polydiorganosiloxane product as Si-O-M where M is an alkali metal atom.
- Solvents are not useful because solvents for the phosphoric acid are not solvents for the siloxanes and solvents for the siloxanes are not solvents for the phosphoric acid.
- solvents for the phosphoric acid are not solvents for the siloxanes and solvents for the siloxanes are not solvents for the phosphoric acid.
- Razzano et al in U.S. Pat. No. 4,177,200, issued Dec. 4, 1979 found a soluble form of phosphoric acid which could be used to neutralize siloxane mixtures containing alkali metal hydroxides.
- Razzano et al found that the known silyl phosphates made by reacting phosphoric acid and octylmethylcyclictetrasiloxane and a small amount of hexamethyldisiloxane could be used to neutralize alkali metal hydroxide in siloxanes.
- Razzano et al reported two difficulties with this silyl phosphate. The viscosity of the silyl phosphate was too high, greater than 500 centipoise at 25° C. and this made it difficult to blend with the siloxane equilibration reaction mixture. The other difficulty reported was that the phosphoric acid content of the silyl phosphate could only achieve a maximum of 10 to 15% by weight.
- Razzano et al describe a silylphosphate made by reacting a siloxane selected from the class of siloxanes of the formula (R 3 Si) 2 O and siloxanes of the formula R 3 Si(R 2 SiO) x OSiR 3 with phosphorous oxyhalogens POCl 3 or POBr 3 where R is a hydrocarbyl radical free of aliphatic unsaturation and x varies from 1 to 20.
- Razzano et al also describe a less preferred method for preparing silylphosphates by reacting phosphoric acid with linear siloxanes at temperatures above 150° C.
- the advantage given for using phosphoric acid in this case is that less of the linear siloxanes are used up in the formation of the silylphosphates.
- the reaction of phosphoric acid with the siloxanes is difficult and does not take place readily unless temperatures 150° C. to 200° C. are reached.
- Razzano et al in a solvent, reacts 1 mole of phosphoric acid with 1.5 moles or more of the siloxane, preferably from 1.5 to 6 moles of the linear siloxanes per mole of phosphoric acid. The by-produced water is distilled off until the reaction is completed taking 1 to 7 hours.
- the silylphosphate produced are (R 3 SiO) 3 P ⁇ O and ⁇ R 3 SiO(R 2 SiO) x ⁇ 3 P ⁇ O where R and x are defined above.
- Razzano et al report that because the reaction is carried out with more difficulty and may not proceed to completion there may be some amounts of monosilyl and disilyl substituted phosphate reaction products and the phosphoric acid will be left with one or two hydroxyl groups.
- the monosilyl and disilyl substituted reaction products may constitute as much as 10% by weight, preferably not more than 5% by weight of the total reaction mixture.
- the silyl phosphate reaction product consisting mostly of trisilyl substituted phosphates is used to neutralize the equilibration siloxane reaction mixtures having alkali metal hydroxide.
- Petersen An improved method for preparing silylphosphates from phosphoric acid and linear low molecular weight polysiloxane is described by Petersen in U.S. Pat. No. 4,125,551, issued Nov. 14, 1978.
- the method taught by Petersen comprises reacting 1 to 30 parts by weight of phosphoric acid with 100 parts by weight of polysiloxane of the formula R(R 2 SiO) w SiR 3 where R is a monovalent hydrocarbon radical and w is from 1 to 100 in the presence of 1.2 to 180% by weight of the total composition of a silyl phosphate catalyst in which the phosphoric acid equivalent in the reaction mixture is from 0.36 to 1.80%.
- Petersen teaches that the reaction is carried out by placing 5 to 25% of the total phosphoric acid in contact with the polysiloxane and the silyl phosphate catalyst, the mixture is heated and the remaining phosphoric acid is added. The reaction began at 150° C. in most cases and varied upwardly during the reaction period until the final temperature of 175° C. to 196° C. was reached. Petersen found that in all cases where no silyl phosphate catalyst was used in the reaction mixture, the reaction did not initiate for a substantial period of time and then the reaction was violent. Petersen describes the product of the method, as a polymer not having a single composition, but a statistical distribution of a variety of structures and molecular weights about a center point.
- the process described by Razzano et al which uses POCl 3 or POBr 3 to make silylphosphate makes trisilyl phosphates and has the disadvantage of by-producing large amounts of triorganochlorosilane or triorganobromosilane.
- the method described by Razzano et al which combines phosphoric acid and siloxane to make silylphosphate is violent as described by Petersen who describes the use of a silylphosphate catalyst to make silylphosphate from phosphoric acid and siloxane.
- Stabilizing is making the catalyst ineffective as an Si-O-Si bond rearrangement catalyst in a practical sense, i.e. the bond rearrangement ability of the metal ion of the catalyst is reduced to a level which produces very small amounts of cyclics when the polydiorganosiloxane is heated.
- silylphosphate which is a mixture containing very little tris(trimethylsilyl) phosphate and which is prepared by a method which does not react violently, does not require a silylphosphate catalyst to produce a silylphosphate smoothly, and does not require the use of high pressure and an autoclave to produce it.
- This invention relates to a method of making a mixture of silylphosphates comprising
- This invention also relates to a mixture of silylphosphates consisting essentially of 10 to 30 weight percent of a monosilyl phosphate of the formula
- Another embodiment of this invention is using the above described mixture of silylphosphates to stabilize the metal ions in a method of making polydiorganosiloxanes using basic compound having a metal ion comprising combining cyclic or low molecular weight linear polydiorganosiloxanes and the basic compound and heating to polymerize the cyclic polydiorganosiloxane, thereafter stabilizing the metal ion in the resulting polydiorganosiloxane using the mixture of silylphosphates.
- Another embodiment of this invention is using, in the above method of stabilizing the metal ion in the polymerization of cyclic or low molecular weight linear polydiorganosiloxanes, a combination of carbon dioxide gas and the mixture of silylphosphate described above.
- the FIGURE contains a schematic cross section of the apparatus during the manufacture of silylphosphate using phosphoric acid and hexamethyldisiloxane.
- the mixture of the silylphosphates of this invention are made by placing liquid hexamethyldisiloxane 3 in a reaction vessel, such as round bottom flask 1, equipped with temperature observation means (thermometer 9), an addition means, such as addition flask 6, agitator 4, and vapor condenser 20.
- the liquid hexamethyldisiloxane 3 is heated to reflux, about 100° C.
- the phosphoric acid 6 is added dropwise, drops 8.
- the phosphoric acid 6 can be syrupy phosphoric acid, i.e. 85 weight percent phosphoric acid and 15 weight percent water.
- hexamethyldisiloxane vapor and the water vapor either from the phosphoric acid-water mixture or by-produced from reaction of phosphoric acid with hexamethyldisiloxane, condenses in vapor condenser 20, the liquefied hexamethyldisiloxane and water fall into the Dean-Stark trap and separate into liquid hexamethyldisiloxane 19 which flows back into the round bottom flask 1, and water 18 which can be withdrawn at appropriate intervals so that it does not flow back into the liquid hexamethyldisiloxane in flask 1.
- An inert gas can be introduced, see direction of inert gas 12, through connecting tube 33 with the flow being controlled by valve 11.
- the inert gas can be dry nitrogen.
- the Dean-Stark trap Prior to the start of the addition of phosphoric acid, the Dean-Stark trap is preferably filled with hexamethyldisiloxane so that the amount of liquid hexamethyldisiloxane in flask 1 remains approximately constant throughout the reaction time.
- Phosphoric acid is added slowly so as to maintain the reflux without loosing control, i.e. the temperature is maintained about 100° C.
- the amount of phosphoric acid added is sufficient to preferably provide from 40 to 65 parts by weight per 100 parts by weight of hexamethyldisiloxane.
- the temperature of the reaction mixture, the material in flask 1 is allowed to increase to a temperature of from about 150° C. to 190° C., preferably about 165° C.
- the unreacted hexamethyldisiloxane is preferably removed.
- the mixture of silylphosphates is susceptible to degradation upon exposure to moisture and thus should be stored in a container which will not allow the ingress of moisture.
- the product of the method of this invention is a mixture of silylphosphates as described above.
- the mixture of silylphosphates may contain a small amount of an unknown by-product material, such as less than 3 weight percent.
- the method of this invention proceeds smoothly, does not require the addition of silylphosphate catalyst, and does not need high pressure or high temperatures.
- the product is a mixture of silylphosphates which contain less trimethylsiloxy groups which are considered contaminates in linear polydiorganosiloxanes.
- the amount of triorganosiloxy units introduced is less than when the tris(trimethylsilyl) phosphate of the prior art is used.
- Triorganosiloxy groups can introduce such groups into the product being stabilized and thus lower amount of trimethylsilyl groups are desirable.
- Polydiorganosiloxane can be made by polymerizing cyclic polydiorganosiloxanes usually having on the average from 3 to 6 diorganosiloxane units per molecule with basic compounds such as metal hydroxides, namely potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, calcium hydroxide, and magnesium hydroxide or metal silanolates derived from the same metals, preferably potassium hydroxide or potassium silanolate.
- This polymerization is an equilibrium reaction and the end product contains a quantity of cyclic polydiorganosiloxanes which, for most purposes, are removed.
- cyclics Removal of these cyclics from the product is usually done by stripping operations under reduced pressure at elevated temperature. Under such conditions cyclics would form as soon as some are removed, because an equilibrium is trying to be maintained and new cyclics are formed by the degradation of the linear polydiorganosiloxane product via Si-O-Si bond rearrangement. To overcome this problem, the metal ion, such as the potassium ion, is made ineffective, such as by stabilizing it.
- the silylphosphates mixture of this invention is a very effective metal ion stabilizer.
- the cyclics can be removed from the polymerization product with only very small amounts of new cyclic formation and in some cases without the formation of new cyclics.
- the polydiorganosiloxane product is therefore stable and the metal ion is essentially ineffective to cause degradation of the polymer chain.
- the amount of the mixture of silylphosphates useful for stabilizing the metal ions in an equilibrium polydiorganosiloxane product is preferably varied to provide at least one phosphate atom per three metal ions. Preferred amounts are at least one phosphate atom per 1.5 metal ions.
- Low molecular weight linear hydroxyl endblocked polydiorganosiloxanes which are condensed with basic catalysts can be stabilized with the silylphosphate mixtures of this invention.
- a very effective metal ion stabilization agent is a combination of carbon dioxide gas and the mixture of silylphosphates. This combination provides the most stable products under conditions of high temperatures, such as above 100° C.
- a silylphosphate mixture was prepared in an apparatus as described by the drawing by placing 280 grams of hexamethyldisiloxane in flask 1 with the Dean-Stark trap 34 filed with hexamethyldisiloxane. Flask 1 was heated to start the hexamethyldisiloxane to reflux, about 100° C., then syrupy phosphoric acid (85 weight percent acid with 15 weight percent water) was added dropwise from addition flask 5 through delivery orifice 27. Water began collecting in the Dean-Stark trap immediately and within 20 minutes 5 cc had collected. After one hour and 20 minutes, the temperature of the liquid hexamethyldisiloxane in flask 1 was 103° C. and the amount of water collected was 13.9 grams.
- the addition of the syrupy phosphoric acid produced a cloudy mixture at first which cleared producing a single phase in about one hour. In two hours and 5 minutes, 200 grams of the syrupy phosphoric acid was added, the temperature was 106° C. The temperature was then increased to 165° C. in 30 minutes and unreacted hexamethyldisiloxane was removed during that period. The total amount of water collected was 44.5 grams. The residue in flask 1 was single phase and clear like water. 406.7 grams of residue was obtained, a yield of 86.8%.
- the residue as determined by NMR was the following mixture: 24.3 weight percent (Me 3 SiO)(OH) 2 P ⁇ O, 70.3 weight percent (Me 3 SiO) 2 (OH)P ⁇ O, 4.3 weight percent (Me 3 SiO) 3 P ⁇ O, and 1.1 weight percent unknown by-product.
- 1,000 parts of a mixture of cyclic polydimethylsiloxanes in which the majority of the cyclics have from 3 to 6 dimethylsiloxane units, 15 parts of dimethylvinylsiloxy endblocked polydimethylsiloxane having about six dimethylsiloxane units per molecule, and potassium silanolate in an amount to provide 50 ppm potassium were polymerized by heating at 165° C. for 100 minutes. Then, 1.75 parts of a mixture of 10 weight percent of Silylphosphate Mixture A and 90 weight percent of cyclic polydimethylsiloxanes was added to stabilize the potassium ion. The stabilization time was five minutes. The mixture was then stripped for 10 minutes at 225° C.
- the resulting polydimethylsiloxane was endblocked with dimethylvinylsiloxy units, had a viscosity of 15.3 Pa.s as determined by ASTM D 1084 Method B (Brookfield viscosimeter), had an hydroxyl index of 0.948, and a weight loss after 3 hours at 150° C. of 0.596 weight percent as determined on a 5 g sample.
- the hydroxyl index is a value obtained by a method which gives an indication of the activity of SiOH present in polysiloxanes by measuring the viscosity before and after catalyzation under controlled conditions.
- a numerical value obtained is defined as the Hydroxyl Index (OH,I). The value is not related to any actual OH value and range from 1 down to 0.1 units.
- a sample of polymer to be tested was brought to 25° C. ⁇ 1° C. and the viscosity was determined using a Brookfield Viscometer with a No. 7 spindle at 50 rpm. The value obtained was recorded as "A".
- a mixture was prepared by mixing the following ingredients to give a yield of about 500 grams: 100 parts of the polymer, 0.90 part of dibutyltindilaurate, and 0.18 part of trimethylsiloxy endblocked poly(methylhydrogensiloxane) having about 0.7 weight percent silicon-bonded hydrogen atoms.
- the mixture was heated to 150° C. ⁇ 1° C. for 1 hour ⁇ 1 minute.
- the mixture was then cooled to 25° C. ⁇ 1° C. and then the viscosity was measured and recorded as "B".
- a silylphosphate mixture was prepared in an apparatus as described by the drawing by placing 1710 grams of hexamethyldisiloxane in flask 1 with the Dean-Stark trap 34 filed with hexamethyldisiloxane. Flask 1 was heated to start the hexamethyldisiloxane to reflux, about 100° C, then syrupy phosphoric acid was added dropwise from addition flask 5 through delivery orifice 27 at a rate of about 1.25 ml per minute. Water began collecting in the Dean-Stark trap immediately and within 2 hours, 45 grams had collected and the temperature of the liquid hexamethyldisiloxane was 92° C.
- the temperature of the liquid hexamethyldisiloxane in flask 1 was 92° C. and the amount of water collected was 109.14 grams.
- 1039 grams of the syrupy phosphoric acid was added, the temperature was 98° C. Increasing the temperature began and within another 30 minutes, the temperature increase to 108° C. and 270 grams of water was removed during that period. The temperature increased to 160° C. in one hour and 30 minutes and unreacted hexamethyldisiloxane was removed. The total amount of water collected was 297.5 grams.
- the residue in flask 1 was single phase and clear like water. 2151 grams of residue was obtained.
- silylphosphate mixture was prepared as described in this example where the residue as determined by NMR was the following mixture: 22.8 weight percent (Me 3 SiO)(OH) 2 P ⁇ O, 70.4 weight percent (Me 3 SiO) 2 (OH)P ⁇ O, 5.6 weight percent (Me 3 SiO) 3 P ⁇ O, and 1.2 weight percent unknown by-product. (Silylphosphate Mixture C).
- a silylphosphate mixture was prepared in an apparatus as described by the drawing by placing 210 grams of hexamethyldisiloxane in flask 1 with the Dean-Stark trap 34 filed with hexamethyldisiloxane. Flask 1 was heated to start the hexamethyldisiloxane refluxing, about 100° C., then syrupy phosphoric acid was added dropwise from addition flask 5 through delivery orifice 27. Water began collecting in the Dean-Stark trap immediately. The total amount of water collected was 29.45 grams. 100 grams of the syrupy phosphoric acid was added, the temperature was then increased to 190° C. and unreacted hexamethyldisiloxane was removed during that period.
- the residue as determined by NMR was the following mixture: 14.6 weight percent (Me 3 SiO)(OH) 2 P ⁇ O, 79.5 weight percent (Me 3 SiO) 2 (OH)P ⁇ O, and 5.9 weight percent (Me 3 SiO) 3 P ⁇ O. (Silylphosphate Mixture D).
- the following mixture was polymerized, 100 parts of cyclic polydimethylsiloxanes as described in Example 1, 0.172 part of dimethylvinylsiloxy endblocked polydimethylsiloxane as described in Example 1, and 0.337 part of potassium silanolate, about 22 ppm K+ in polymer.
- the mixture was polymerized at 175° C. for about 2.5 hours producing a gum/cyclic mixture of polydimethylsiloxane with dimethylvinylsiloxy endblocks and then it was stabilized by one of two methods.
- the silylphosphate mixture used (Silylphosphate Mixture E) in the following methods was a mixture of Silylphosphate Mixture C and Silylphosphate Mixture D in a 50/50 weight mixture.
- the gum/cyclic mixture was stabilized by adding 0.714 part of the silylphosphate mixture as described in Example 3 which was a mixture of 1.36 weight percent of the Silylphosphate Mixture E in cyclic polydimethylsiloxanes.
- the gum/cyclic mixture was stabilized by adding 0.714 part of the silylphosphate mixture of Example 3 which was a mixture of 1.36 weight percent of the silylphosphate mixture E in cyclic polydimethylsiloxanes and 0.028 part per hour of carbon dioxide gas.
- each method took about 10 minutes.
- Each gum/cyclic mixture was stripped of residual cyclics to a weight loss of 1.65 weight percent which was determined by heating a 5 g sample for 3 hours at 150° C. The plasticity and activity of resulting gum from each stabilization method was determined.
- the plasticity of the gum from the first method of stabilization was 48 and the plasticity of the gum from the second method of stabilization was 58.
- the plasticity of the gum was measured by ASTM D926 and the values reported were in thousands of an inch.
- the activity of the gum from the first method of stabilization was 68 and the activity of the gum from the second method of stabilization was 15.
- the activity of the gum is an indication of the amount of silicon bonded hydroxyl group and the lower the activity number the lower the hydroxyl group content. This example showed that the lowest activity and most stable polydimethylsiloxane was obtained by using a combination of silylphosphate and carbon dioxide.
- the activity of a silicone polymer is estimated by measuring the increase in plasticity of the polymer before and after compounding with tetraisopropyl titanate and comparing the ratio obtained with the ratio of a standard polymer. Activities in the range of 0 to 75 can be determined by this method.
- a Brabender PLAST-CORD made by C. W. Brabender Instruments Inc., Southhackensack, New Jersey and equipped with a type 6 mixing head in a room controlled to a temperature of 23° C. ⁇ 1° C. and 50% ⁇ 5% relative humidity was used.
- a sample of the polymer was placed in this room for one hour before the test was conducted.
- 42.0 ⁇ 0.1 g of polymer was feed into the mixing chamber of the Brabender at a mixing speed of 15 ⁇ 1 rpm.
- 0.08 ⁇ 0.01 g tetraisopropyltitanate was added and the mixing was continued for 10 ⁇ 0.2 minutes with the lid open. Then two 4.2 g ⁇ 0.01 g was removed and allowed to rest for 10 minutes.
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Abstract
Silylphosphate mixtures are prepared by slowly adding phosphoric acid to hexamethyldisiloxane under reflux while removing the by-produced water and after the phosphoric acid is added, the temperture is increased to from 150° C. to 170° C. to recover the silylphosphate mixture residue. The mixture has from 10 to 30 weight percent of a monosilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}(HO).sub.2 P═O,
65 to 85 weight percent of a disilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}.sub.2 (HO)P═O,
and 2 to 7 weight percent of a trisilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}.sub.3 P═O.
These silylphosphate mixtures are useful in stabilizing basic polymerization catalyst such as potassium hydroxide or potassium silanolate and can either be used effectively per se or in combination with carbon dioxide.
Description
1. Field of the Invention
This invention relates to a method of making silylphosphates, to the silylphosphates, and their use in stabilizing alkali metals and alkaline earth metals in polyorganosiloxanes.
2. Background Information
Polydiorganosiloxanes are used in many products, such as various kinds of silicone rubbers and fluids. Many of the products require property stability under high temperature exposure to function properly in their intended utility. Because the polydiorganosiloxanes are most often made by a polymerization process involving strong base equilibration of linear polydiorganosiloxane hydrolyzates or cyclic polydiorganosiloxanes and because this equilibration proceeds via a silicon-oxygen-silicon bond breakage and reformation, the basic polymerization catalyst used must be rendered ineffective if it remains in the final product. The amount of the basic compound is very small and difficult to remove at reasonable cost, so techniques have been developed to reduce the catalyst's harmful effects. The methods of neutralizing the catalyst's activity have varied effectiveness and each method seems to have one or more disadvantages.
Polydiorganosiloxane can be prepared by the well known process of converting low molecular weight linear polydiorganosiloxanes and cyclic polydiorganosiloxanes by heating above 100° C. in the presence of potassium hydroxide or potassium silanolate. Other known alkali metal catalysts for this kind of polymerization, are sodium hydroxide, cesium hydroxide, lithium hydroxide, and their corresponding silanolates or siloxanates. In the case of the cyclic polydiorganosiloxane polymerization, a ring opening reaction takes place with the formation of linear polymers. Most often, such as in the case of polydimethylsiloxane the resulting product of the equilibration reaction is about 85% linear polymer and 15% cyclic polydimethylsiloxanes. The presence of the cyclic siloxanes in products is undesirable because they are of low molecular weight and have a sufficiently high vapor pressure to cause problems during use, such as problems in closed or semiclosed conditions where electrical or electronic equipment is in close proximity with silicone rubber and therefore, these cyclic siloxanes should be removed. The most convenient method of removing these cyclic siloxanes is by heating under reduced pressure, however, if the basic catalyst's activity is not hindered, the distillation process will continuously generate cyclic siloxanes; as they are removed from the linear polydiorganosiloxane product more will be formed because of the reaction's potential to go to equilibrium. Therefore, it is important even in the preparation of the linear polydiorganosiloxanes to stabilize the basic catalyst. Various methods of stabilizing this basic catalyst have been used in the past. Terms, such as neutralizing the catalyst or killing the catalyst have been used in the art with various meanings. The inventors in this application use the term stabilizing the catalyst or stabilization of the catalyst to mean reducing the deleterious activity of metal ions resulting from polymerization reactions, thereby making them ineffective, for the most part, to cause Si-O-Si bond rearrangement and cyclic formation.
One method of neutralizing the basic catalyst is the use of various types of acids. One difficulty with strong acids such as hydrochloric acid or sulfuric acid is that the amount of the acid used must be very carefully controlled because either excess base or excess acid will be detrimental to the final linear polydiorganosiloxanes stability. Both acids and bases are known equilibration catalysts, thus both produce similar results if left in the product. It is known that excess acid will cause degradation of the product similar to the degradation resulting from base such as alkali metal hydroxides. It is difficult to get the base completely neutral using a strong acid and would be very expensive and time consuming. Weak acids have also been used, such as acetic acid, but these acids have a similar problem.
Phosphoric acid, because it is a buffering kind of acid, has the ability to overcome the strong acid problem of neutralizing the basic catalysts used in the preparation of linear polydiorganosiloxane through an equilibration reaction. However, phosphoric acid is not soluble in the linear polydiorganosiloxane or in the cyclic polydiorganosiloxanes and to be an effective catalyst stabilizer it needs to be soluble so that it can get to the alkali metal ions which are often located, when equilibrium is reached, on the terminal silicon atoms of the polydiorganosiloxane product as Si-O-M where M is an alkali metal atom. Solvents are not useful because solvents for the phosphoric acid are not solvents for the siloxanes and solvents for the siloxanes are not solvents for the phosphoric acid. To overcome the difficulty with the insolubility of the phosphoric acid, Razzano et al in U.S. Pat. No. 4,177,200, issued Dec. 4, 1979, found a soluble form of phosphoric acid which could be used to neutralize siloxane mixtures containing alkali metal hydroxides. Razzano et al found that the known silyl phosphates made by reacting phosphoric acid and octylmethylcyclictetrasiloxane and a small amount of hexamethyldisiloxane could be used to neutralize alkali metal hydroxide in siloxanes. However, Razzano et al reported two difficulties with this silyl phosphate. The viscosity of the silyl phosphate was too high, greater than 500 centipoise at 25° C. and this made it difficult to blend with the siloxane equilibration reaction mixture. The other difficulty reported was that the phosphoric acid content of the silyl phosphate could only achieve a maximum of 10 to 15% by weight.
Razzano et al describe a silylphosphate made by reacting a siloxane selected from the class of siloxanes of the formula (R3 Si)2 O and siloxanes of the formula R3 Si(R2 SiO)x OSiR3 with phosphorous oxyhalogens POCl3 or POBr3 where R is a hydrocarbyl radical free of aliphatic unsaturation and x varies from 1 to 20. Razzano et al also describe a less preferred method for preparing silylphosphates by reacting phosphoric acid with linear siloxanes at temperatures above 150° C. The advantage given for using phosphoric acid in this case is that less of the linear siloxanes are used up in the formation of the silylphosphates. According to Razzano et al, the reaction of phosphoric acid with the siloxanes is difficult and does not take place readily unless temperatures 150° C. to 200° C. are reached. Razzano et al, in a solvent, reacts 1 mole of phosphoric acid with 1.5 moles or more of the siloxane, preferably from 1.5 to 6 moles of the linear siloxanes per mole of phosphoric acid. The by-produced water is distilled off until the reaction is completed taking 1 to 7 hours. The silylphosphate produced are (R3 SiO)3 P═O and {R3 SiO(R2 SiO)x }3 P═O where R and x are defined above. Razzano et al report that because the reaction is carried out with more difficulty and may not proceed to completion there may be some amounts of monosilyl and disilyl substituted phosphate reaction products and the phosphoric acid will be left with one or two hydroxyl groups. The monosilyl and disilyl substituted reaction products may constitute as much as 10% by weight, preferably not more than 5% by weight of the total reaction mixture. The silyl phosphate reaction product consisting mostly of trisilyl substituted phosphates is used to neutralize the equilibration siloxane reaction mixtures having alkali metal hydroxide.
An improved method for preparing silylphosphates from phosphoric acid and linear low molecular weight polysiloxane is described by Petersen in U.S. Pat. No. 4,125,551, issued Nov. 14, 1978. The method taught by Petersen comprises reacting 1 to 30 parts by weight of phosphoric acid with 100 parts by weight of polysiloxane of the formula R(R2 SiO)w SiR3 where R is a monovalent hydrocarbon radical and w is from 1 to 100 in the presence of 1.2 to 180% by weight of the total composition of a silyl phosphate catalyst in which the phosphoric acid equivalent in the reaction mixture is from 0.36 to 1.80%.
Petersen teaches that the reaction is carried out by placing 5 to 25% of the total phosphoric acid in contact with the polysiloxane and the silyl phosphate catalyst, the mixture is heated and the remaining phosphoric acid is added. The reaction began at 150° C. in most cases and varied upwardly during the reaction period until the final temperature of 175° C. to 196° C. was reached. Petersen found that in all cases where no silyl phosphate catalyst was used in the reaction mixture, the reaction did not initiate for a substantial period of time and then the reaction was violent. Petersen describes the product of the method, as a polymer not having a single composition, but a statistical distribution of a variety of structures and molecular weights about a center point.
The process described by Razzano et al which uses POCl3 or POBr3 to make silylphosphate makes trisilyl phosphates and has the disadvantage of by-producing large amounts of triorganochlorosilane or triorganobromosilane. The method described by Razzano et al which combines phosphoric acid and siloxane to make silylphosphate is violent as described by Petersen who describes the use of a silylphosphate catalyst to make silylphosphate from phosphoric acid and siloxane.
Czechoslovakian Patent No. 173,332, published May 28, 1976, to Dvorak et al teach that making tris(trimethylsilyl)phosphate in high yields from phosphoric acid and hexamethyldisiloxane requires high pressure and high temperature. For example, the reaction is carried out at a pressure of 1 to 10 atmospheres at a temperature of 200° C. for three hours.
An extensive search for a material useful for stabilizing the basic catalyst used in the preparation of linear polydiorganosiloxanes without the problems associated with the its preparation was conducted by the inventors. Stabilizing is making the catalyst ineffective as an Si-O-Si bond rearrangement catalyst in a practical sense, i.e. the bond rearrangement ability of the metal ion of the catalyst is reduced to a level which produces very small amounts of cyclics when the polydiorganosiloxane is heated. They discovered a new silylphosphate which is a mixture containing very little tris(trimethylsilyl) phosphate and which is prepared by a method which does not react violently, does not require a silylphosphate catalyst to produce a silylphosphate smoothly, and does not require the use of high pressure and an autoclave to produce it.
This invention relates to a method of making a mixture of silylphosphates comprising
heating hexamethyldisiloxane to reflux in a closed container equipped with a condenser means, a water trapping means, and a controllable addition means, the hexamethyldisiloxane at reflux existing with a liquid phase and a vapor phase in equilibrium in the closed container,
slowly adding phosphoric acid to the hexamethyldisiloxane liquid phase with the controllable addition means while maintaining reflux, the phosphoric acid addition is continued until 40 to 65 parts by weight are added per 100 parts by weight of hexamethyldisiloxane,
collecting by-produced water with the water trapping means and removing the collected water at a rate sufficient to keep the water from returning to the liquid phase hexamethyldisiloxane,
allowing the temperature of the liquid phase hexamethyldisiloxane to increase to a temperature in the range of 150° C. to 190° C. after the addition of the phosphoric acid is completed,
recovering a mixture of silylphosphates.
This invention also relates to a mixture of silylphosphates consisting essentially of 10 to 30 weight percent of a monosilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}(HO).sub.2 P═O,
65 to 85 weight percent of a disilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}.sub.2 (HO)P═O,
and 2 to 7 weight percent of a trisilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}.sub.3 P═O.
Another embodiment of this invention is using the above described mixture of silylphosphates to stabilize the metal ions in a method of making polydiorganosiloxanes using basic compound having a metal ion comprising combining cyclic or low molecular weight linear polydiorganosiloxanes and the basic compound and heating to polymerize the cyclic polydiorganosiloxane, thereafter stabilizing the metal ion in the resulting polydiorganosiloxane using the mixture of silylphosphates.
Another embodiment of this invention is using, in the above method of stabilizing the metal ion in the polymerization of cyclic or low molecular weight linear polydiorganosiloxanes, a combination of carbon dioxide gas and the mixture of silylphosphate described above.
The FIGURE contains a schematic cross section of the apparatus during the manufacture of silylphosphate using phosphoric acid and hexamethyldisiloxane.
1: 4-necked round bottom flask
2: heating mantle
3: liquid hexamethyldisiloxane
4: agitator
5: addition flask with pressure equalizer
6: phosphoric acid
7: addition flow control valve
8: phosphoric acid drops dropping into liquid hexamethyldisiloxane
9: thermometer
10: temperature controller-transmitter
11: inert gas flow control valve
12: inert gas flow direction
13: electrical switch with voltage adjustment
14: electrical connector to electrical power source
15: power source for driving agitator 4
16: drain valve
17: discard water from drain valve 16
18: water
19: liquid hexamethyldisiloxane from vapor condenser 20
20: vapor condenser
21: inert gas bubbler
22: inert gas outlet tube
23: cooling water inlet
24: cooling water outlet
25: electrical control wire
26: shaft connecting agitator 4 and power source 15
27: phosphoric acid delivery orifice
28: flask neck
29: flask neck
30: flask neck
31: flask neck
32: electrical cord
33: connecting tube
34: Dean-Stark trap receiver
35: liquid hexamethyldisiloxane flowing back into 4-necked round bottom flask 1
36: inert gas bubbles
37: pressure equalizer line
38: tube
39: inert gas inlet
The mixture of the silylphosphates of this invention are made by placing liquid hexamethyldisiloxane 3 in a reaction vessel, such as round bottom flask 1, equipped with temperature observation means (thermometer 9), an addition means, such as addition flask 6, agitator 4, and vapor condenser 20. The liquid hexamethyldisiloxane 3 is heated to reflux, about 100° C. When the hexamethyldisiloxane 3 is at reflux, the phosphoric acid 6 is added dropwise, drops 8. The phosphoric acid 6 can be syrupy phosphoric acid, i.e. 85 weight percent phosphoric acid and 15 weight percent water. As soon as the first drops 8 of phosphoric acid are added, water 18 begins to collect in the Dean-Stark trap 34. The reflux is maintained through an interacting combination of thermometer 9, temperature controller 10, connecting wire 25, electrical switch with voltage adjustment 13, and heating mantle 2. The amount of heating is controlled through this arrangement to maintain the reflux at a constant rate. The addition of phosphoric acid 6 will vary depending upon the amounts involved. The phosphoric acid is added at a rate so that the reflux rate is maintained. During the addition of phosphoric acid 6, the liquid hexamethyldisiloxane is stirred with agitator 4. The amount of agitation is not critical but should be sufficient to stir the liquid hexamethyldisiloxane 3 and keep the phosphoric acid from settling to the bottom of flask 1. The hexamethyldisiloxane vapor and the water vapor, either from the phosphoric acid-water mixture or by-produced from reaction of phosphoric acid with hexamethyldisiloxane, condenses in vapor condenser 20, the liquefied hexamethyldisiloxane and water fall into the Dean-Stark trap and separate into liquid hexamethyldisiloxane 19 which flows back into the round bottom flask 1, and water 18 which can be withdrawn at appropriate intervals so that it does not flow back into the liquid hexamethyldisiloxane in flask 1. An inert gas can be introduced, see direction of inert gas 12, through connecting tube 33 with the flow being controlled by valve 11. The inert gas can be dry nitrogen. Prior to the start of the addition of phosphoric acid, the Dean-Stark trap is preferably filled with hexamethyldisiloxane so that the amount of liquid hexamethyldisiloxane in flask 1 remains approximately constant throughout the reaction time.
Phosphoric acid is added slowly so as to maintain the reflux without loosing control, i.e. the temperature is maintained about 100° C. The amount of phosphoric acid added is sufficient to preferably provide from 40 to 65 parts by weight per 100 parts by weight of hexamethyldisiloxane. After the addition of the phosphoric acid is completed, the temperature of the reaction mixture, the material in flask 1, is allowed to increase to a temperature of from about 150° C. to 190° C., preferably about 165° C. During the period of time when the temperature of the reaction mixture is increasing to a temperature of from 150° C. to 190° C., the unreacted hexamethyldisiloxane is preferably removed. This can be done through the Dean-Stark trap 34 via valve 16. After the unreacted hexamethyldisiloxane is removed, the residue remaining in flask 1 is cooled and if it is to be stored for use at a later time, it is packaged in an airtight package. The mixture of silylphosphates is susceptible to degradation upon exposure to moisture and thus should be stored in a container which will not allow the ingress of moisture. The product of the method of this invention is a mixture of silylphosphates as described above. The mixture of silylphosphates may contain a small amount of an unknown by-product material, such as less than 3 weight percent.
The method of this invention proceeds smoothly, does not require the addition of silylphosphate catalyst, and does not need high pressure or high temperatures. The product is a mixture of silylphosphates which contain less trimethylsiloxy groups which are considered contaminates in linear polydiorganosiloxanes. For example, when polydiorganosiloxanes are stabilized with the mixture of silylphosphates of this invention, the amount of triorganosiloxy units introduced is less than when the tris(trimethylsilyl) phosphate of the prior art is used. Triorganosiloxy groups can introduce such groups into the product being stabilized and thus lower amount of trimethylsilyl groups are desirable.
The mixture of silylphosphates is useful as a stabilizing agent for metal ions. Polydiorganosiloxane can be made by polymerizing cyclic polydiorganosiloxanes usually having on the average from 3 to 6 diorganosiloxane units per molecule with basic compounds such as metal hydroxides, namely potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, calcium hydroxide, and magnesium hydroxide or metal silanolates derived from the same metals, preferably potassium hydroxide or potassium silanolate. This polymerization is an equilibrium reaction and the end product contains a quantity of cyclic polydiorganosiloxanes which, for most purposes, are removed. Removal of these cyclics from the product is usually done by stripping operations under reduced pressure at elevated temperature. Under such conditions cyclics would form as soon as some are removed, because an equilibrium is trying to be maintained and new cyclics are formed by the degradation of the linear polydiorganosiloxane product via Si-O-Si bond rearrangement. To overcome this problem, the metal ion, such as the potassium ion, is made ineffective, such as by stabilizing it. The silylphosphates mixture of this invention is a very effective metal ion stabilizer. The cyclics can be removed from the polymerization product with only very small amounts of new cyclic formation and in some cases without the formation of new cyclics. The polydiorganosiloxane product is therefore stable and the metal ion is essentially ineffective to cause degradation of the polymer chain. The amount of the mixture of silylphosphates useful for stabilizing the metal ions in an equilibrium polydiorganosiloxane product is preferably varied to provide at least one phosphate atom per three metal ions. Preferred amounts are at least one phosphate atom per 1.5 metal ions. Low molecular weight linear hydroxyl endblocked polydiorganosiloxanes which are condensed with basic catalysts can be stabilized with the silylphosphate mixtures of this invention.
A very effective metal ion stabilization agent is a combination of carbon dioxide gas and the mixture of silylphosphates. This combination provides the most stable products under conditions of high temperatures, such as above 100° C.
The following examples are presented for illustrative purposes and should not be construed as limiting this invention which is properly delineated in the claims. In the following examples, "part" or "parts" are "part by weight" and "parts by weight" respectively, viscosities are at 25° C. unless otherwise specified, and Me is methyl radical.
A silylphosphate mixture was prepared in an apparatus as described by the drawing by placing 280 grams of hexamethyldisiloxane in flask 1 with the Dean-Stark trap 34 filed with hexamethyldisiloxane. Flask 1 was heated to start the hexamethyldisiloxane to reflux, about 100° C., then syrupy phosphoric acid (85 weight percent acid with 15 weight percent water) was added dropwise from addition flask 5 through delivery orifice 27. Water began collecting in the Dean-Stark trap immediately and within 20 minutes 5 cc had collected. After one hour and 20 minutes, the temperature of the liquid hexamethyldisiloxane in flask 1 was 103° C. and the amount of water collected was 13.9 grams. The addition of the syrupy phosphoric acid produced a cloudy mixture at first which cleared producing a single phase in about one hour. In two hours and 5 minutes, 200 grams of the syrupy phosphoric acid was added, the temperature was 106° C. The temperature was then increased to 165° C. in 30 minutes and unreacted hexamethyldisiloxane was removed during that period. The total amount of water collected was 44.5 grams. The residue in flask 1 was single phase and clear like water. 406.7 grams of residue was obtained, a yield of 86.8%. The residue as determined by NMR (neuclear magnetic resonance) was the following mixture: 24.3 weight percent (Me3 SiO)(OH)2 P═O, 70.3 weight percent (Me3 SiO)2 (OH)P═O, 4.3 weight percent (Me3 SiO)3 P═O, and 1.1 weight percent unknown by-product.
1,000 parts of a mixture of cyclic polydimethylsiloxanes in which the majority of the cyclics have from 3 to 6 dimethylsiloxane units, 15 parts of dimethylvinylsiloxy endblocked polydimethylsiloxane having about six dimethylsiloxane units per molecule, and potassium silanolate in an amount to provide 50 ppm potassium were polymerized by heating at 165° C. for 100 minutes. Then, 1.75 parts of a mixture of 10 weight percent of Silylphosphate Mixture A and 90 weight percent of cyclic polydimethylsiloxanes was added to stabilize the potassium ion. The stabilization time was five minutes. The mixture was then stripped for 10 minutes at 225° C. and then cooled to room temperature. The resulting polydimethylsiloxane was endblocked with dimethylvinylsiloxy units, had a viscosity of 15.3 Pa.s as determined by ASTM D 1084 Method B (Brookfield viscosimeter), had an hydroxyl index of 0.948, and a weight loss after 3 hours at 150° C. of 0.596 weight percent as determined on a 5 g sample.
The hydroxyl index is a value obtained by a method which gives an indication of the activity of SiOH present in polysiloxanes by measuring the viscosity before and after catalyzation under controlled conditions. A numerical value obtained is defined as the Hydroxyl Index (OH,I). The value is not related to any actual OH value and range from 1 down to 0.1 units. A sample of polymer to be tested was brought to 25° C.±1° C. and the viscosity was determined using a Brookfield Viscometer with a No. 7 spindle at 50 rpm. The value obtained was recorded as "A". A mixture was prepared by mixing the following ingredients to give a yield of about 500 grams: 100 parts of the polymer, 0.90 part of dibutyltindilaurate, and 0.18 part of trimethylsiloxy endblocked poly(methylhydrogensiloxane) having about 0.7 weight percent silicon-bonded hydrogen atoms. The mixture was heated to 150° C.±1° C. for 1 hour±1 minute. The mixture was then cooled to 25° C.±1° C. and then the viscosity was measured and recorded as "B". The hydroxyl index (OH,I) was calculated to three decimals using the following formula OH,I=A/B.
A silylphosphate mixture was prepared in an apparatus as described by the drawing by placing 1710 grams of hexamethyldisiloxane in flask 1 with the Dean-Stark trap 34 filed with hexamethyldisiloxane. Flask 1 was heated to start the hexamethyldisiloxane to reflux, about 100° C, then syrupy phosphoric acid was added dropwise from addition flask 5 through delivery orifice 27 at a rate of about 1.25 ml per minute. Water began collecting in the Dean-Stark trap immediately and within 2 hours, 45 grams had collected and the temperature of the liquid hexamethyldisiloxane was 92° C. After 4 hours and 15 minutes, the temperature of the liquid hexamethyldisiloxane in flask 1 was 92° C. and the amount of water collected was 109.14 grams. In 7 hours, 1039 grams of the syrupy phosphoric acid was added, the temperature was 98° C. Increasing the temperature began and within another 30 minutes, the temperature increase to 108° C. and 270 grams of water was removed during that period. The temperature increased to 160° C. in one hour and 30 minutes and unreacted hexamethyldisiloxane was removed. The total amount of water collected was 297.5 grams. The residue in flask 1 was single phase and clear like water. 2151 grams of residue was obtained. The residue as determined by NMR was the following mixture: 20.1 weight percent (Me3 SiO)(OH)2 P═O, 72.7 weight percent (Me3 SiO)2 (OH)P═O, 6.2 weight percent (Me3 SiO)3 P═O, and 1.0 weight percent unknown by-product. (Silylphosphate Mixture B).
Another silylphosphate mixture was prepared as described in this example where the residue as determined by NMR was the following mixture: 22.8 weight percent (Me3 SiO)(OH)2 P═O, 70.4 weight percent (Me3 SiO)2 (OH)P═O, 5.6 weight percent (Me3 SiO)3 P═O, and 1.2 weight percent unknown by-product. (Silylphosphate Mixture C).
A silylphosphate mixture was prepared in an apparatus as described by the drawing by placing 210 grams of hexamethyldisiloxane in flask 1 with the Dean-Stark trap 34 filed with hexamethyldisiloxane. Flask 1 was heated to start the hexamethyldisiloxane refluxing, about 100° C., then syrupy phosphoric acid was added dropwise from addition flask 5 through delivery orifice 27. Water began collecting in the Dean-Stark trap immediately. The total amount of water collected was 29.45 grams. 100 grams of the syrupy phosphoric acid was added, the temperature was then increased to 190° C. and unreacted hexamethyldisiloxane was removed during that period. The residue as determined by NMR was the following mixture: 14.6 weight percent (Me3 SiO)(OH)2 P═O, 79.5 weight percent (Me3 SiO)2 (OH)P═O, and 5.9 weight percent (Me3 SiO)3 P═O. (Silylphosphate Mixture D).
Five polymerizations (runs) were carried out and each one was stabilized by a different technique as described below. In each polymerization 1,000 parts of a mixture of cyclic polydimethylsiloxanes in which the majority of the cyclics have from 3 to 6 dimethylsiloxane units was heated to 165° C. and then 25 parts of dimethylvinylsiloxy endblocked polydimethylsiloxane having about six dimethylsiloxane units per molecule, and potassium silanolate in an amount to provide 30 ppm potassium were added and then polymerized by heating at 165° C. to 185° C. for 60 minutes. Then, in Run 1, carbon dioxide was used to stabilize the potassium ion (comparative example). In Run 2, a mixture of 8.7 parts of trimethylchlorosilane in 91.3 parts of cyclic polydimethylsiloxanes was added to the polymerization product in an amount to provide one chlorine atom per one potassium ion (comparative example). In Run 3, a mixture of 4.8 parts of acetic acid in 95.2 parts of cyclic polydimethylsiloxanes was added to the polymerization product in an amount to provide one acetic acid molecule per one potassium ion (comparative example). In Run 4, a mixture of 83.2 parts of cyclic polydimethylsiloxanes and 16.8 parts of a purchased silylphosphate which was a mixture of 7 weight percent (Me3 SiO)2 (OH)P═O, 88.7 weight percent (Me3 SiO)3 P═O, and 4.3 weight percent {(Me3 SiO)2 P═O}2 O was added to provide one phosphorus atom per 1.5 potassium ions (comparative example). In Run 5, a mixture of 87.1 parts of cyclic polydimethylsiloxanes and 12.9 parts of Silylphosphate Mixture D was added to provide one phosphorus atom per 1.5 potassium ions. The stabilization time was five minutes. The mixture was then stripped for 10 minutes at 225° C. and then cooled to room temperature. The resulting polydimethylsiloxane was endblocked with dimethylvinylsiloxy units. Table I shows the results obtained in each run. The yield, viscosity by ASTM D 1084 Method B, hydroxyl index by the method as described above, cyclic generation as described below, decomposition rate as described below, and a weight loss after 3 hours at 150° C. on a 5 g sample were determined and are shown in Table I.
TABLE 1 ______________________________________ PROPERTY RUN 1RUN 2RUN 3 RUN 4RUN 5 ______________________________________ Yield, g 692 900 884 888 890 Viscosity, 1.58 2.76 2.70 3.12 3.64 Pa · s OH Index 0.86 0.69 0.85 0.83 0.84 Weight Loss 1.59 1.54 1.39 1.23 1.02 Cyclic 18.4 -1.65 0.41 -0.8 -0.74 Generation, %* Decomposition 9.6 -- -- 0.021 0.0952 Rate, %/min** ______________________________________ *Cyclic generation was determined by the following formula in which 13.7 was the assumed equilibrium concentration (wt %) of cyclic siloxanes: Cyclic generation ##STR1## **The decomposition rate was determined by isothermal thermogravimetric analysis (TGA) at 300° C. with a helium gas flow of 100 cc/min and the instantaneous derivative of the weight loss vs. time was taken after 30 minutes exposure.
The results of this example showed that the silylphosphates of this invention (Run 5) resulted in a lower hydroxyl index than the polymer stabilized with the carbon dioxide (Run 1), and had a lower weight loss than Runs 1, 2, 3, and 4 resulting in a polydimethylsiloxane which was more stable.
The following mixture was polymerized, 100 parts of cyclic polydimethylsiloxanes as described in Example 1, 0.172 part of dimethylvinylsiloxy endblocked polydimethylsiloxane as described in Example 1, and 0.337 part of potassium silanolate, about 22 ppm K+ in polymer. The mixture was polymerized at 175° C. for about 2.5 hours producing a gum/cyclic mixture of polydimethylsiloxane with dimethylvinylsiloxy endblocks and then it was stabilized by one of two methods.
The silylphosphate mixture used (Silylphosphate Mixture E) in the following methods was a mixture of Silylphosphate Mixture C and Silylphosphate Mixture D in a 50/50 weight mixture. In the first method, the gum/cyclic mixture was stabilized by adding 0.714 part of the silylphosphate mixture as described in Example 3 which was a mixture of 1.36 weight percent of the Silylphosphate Mixture E in cyclic polydimethylsiloxanes.
In the second method, the gum/cyclic mixture was stabilized by adding 0.714 part of the silylphosphate mixture of Example 3 which was a mixture of 1.36 weight percent of the silylphosphate mixture E in cyclic polydimethylsiloxanes and 0.028 part per hour of carbon dioxide gas.
In each method, the stabilization process took about 10 minutes. Each gum/cyclic mixture was stripped of residual cyclics to a weight loss of 1.65 weight percent which was determined by heating a 5 g sample for 3 hours at 150° C. The plasticity and activity of resulting gum from each stabilization method was determined.
The plasticity of the gum from the first method of stabilization was 48 and the plasticity of the gum from the second method of stabilization was 58. The plasticity of the gum was measured by ASTM D926 and the values reported were in thousands of an inch.
The activity of the gum from the first method of stabilization was 68 and the activity of the gum from the second method of stabilization was 15. The activity of the gum is an indication of the amount of silicon bonded hydroxyl group and the lower the activity number the lower the hydroxyl group content. This example showed that the lowest activity and most stable polydimethylsiloxane was obtained by using a combination of silylphosphate and carbon dioxide.
The activity of a silicone polymer is estimated by measuring the increase in plasticity of the polymer before and after compounding with tetraisopropyl titanate and comparing the ratio obtained with the ratio of a standard polymer. Activities in the range of 0 to 75 can be determined by this method.
A Brabender PLAST-CORD, made by C. W. Brabender Instruments Inc., South Hackensack, New Jersey and equipped with a type 6 mixing head in a room controlled to a temperature of 23° C.±1° C. and 50% ±5% relative humidity was used. A sample of the polymer was placed in this room for one hour before the test was conducted. 42.0±0.1 g of polymer was feed into the mixing chamber of the Brabender at a mixing speed of 15±1 rpm. To the mixing polymer 0.08±0.01 g tetraisopropyltitanate was added and the mixing was continued for 10±0.2 minutes with the lid open. Then two 4.2 g ±0.01 g was removed and allowed to rest for 10 minutes. At the same time, two 4.2 g samples of uncatalyzed polymer were made and allowed to rest for 10 minutes. The plasticity as described above of the four samples were measured in the order as weighed. The average of the two uncatalyzed polymer samples was designated "I" and the average of the two catalyzed polymer samples was designated "F". The activity was calculated by the following formula
Activity=(R-1)100
where R=F/I.
Claims (6)
1. A method of making a mixture of silylphosphates comprising
heating hexamethyldisiloxane to reflux in a closed container equipped with a condenser means, a water trapping means, and a controllable addition means, the hexamethyldisiloxane at reflux existing with a liquid phase and a vapor phase in equilibrium in the closed container,
slowly adding phosphoric acid to the hexamethyldisiloxane liquid phase with the controllable addition means while maintaining reflux, the phosphoric acid addition is continued until 40 to 65 parts by weight are added per 100 parts by weight of hexamethyldisiloxane,
collecting by-produced water with the water trapping means and removing the collected water at a rate sufficient to keep the water from returning to the liquid phase hexamethyldisiloxane,
allowing the temperature of the liquid phase hexamethyldisiloxane to increase to a temperature in the range of from 150° C. to 190° C. after the addition of phosphoric acid is completed,
recovering a mixture of silylphosphates.
2. The method in accordance with claim 1 in which unreacted hexamethyldisiloxane is removed from the mixture of silylphosphates during the period of time as the temperature is increasing to a temperature of from 150° C. to 190° C.
3. The method in accordance with claim 2 in which the recovered mixture of silylphosphate is cooled and packaged in an airtight container for storage.
4. A mixture of silylphosphates consisting essentially of 10 to 30 weight percent of a monosilyl phosphate of the formula
{(CH3).sub.3 SiO}(HO).sub.2 P═O,
65 to 85 weight percent of a disilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}.sub.2 (HO)P═O,
and 2 to 7 weight percent of a trisilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}.sub.3 P═O.
5. In a method of making polydiorganosiloxanes with a basic compound having a metal ion comprising combining cyclic polydiorganosiloxanes and the basic compound and heating to polymerize the cyclic polydiorganosiloxanes or heating to condense low molecular weight hydroxy endblocked polydiorganosiloxanes, thereafter stabilizing the metal ion in the resulting polydiorganosiloxane using a stabilizing material, the improvement consisting of using as the stabilizing material, a mixture of silylphosphates consisting essentially of 10 to 30 weight percent of a monosilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}(HO).sub.2 P═O,
65 to 85 weight percent of a disilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}.sub.2 (HO)P═O,
and 2 to 7 weight percent of a trisilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}.sub.3 P═O.
6. In a method of making polydiorganosiloxanes with a basic compound having a metal ion comprising combining cyclic polydiorganosiloxanes and the basic compound and heating to polymerize the cyclic polydiorganosiloxanes or heating to condense low molecular weight hydroxyl endblocked linear polydiorganosiloxanes, thereafter stabilizing the metal ion in the resulting polydiorganosiloxane using a stabilizing material, the improvement consisting of using as the stabilizing material, a combination of carbon dioxide gas and a mixture of silylphosphates consisting essentially of 10 to 30 weight percent of a monosilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}(HO).sub.2 P═O,
65 to 85 weight percent of a disilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}.sub.2 (HO)P═O,
and 2 to 7 weight percent of a trisilyl phosphate of the formula
{(CH.sub.3).sub.3 SiO}.sub.3 P═O.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/622,051 US5041586A (en) | 1990-11-29 | 1990-11-29 | Method of preparing a silyphosphate mixture, silyphosphate mixture and its use in stabilizing metal silanolates in siloxane polymers |
EP91304296A EP0488490B1 (en) | 1990-11-29 | 1991-05-14 | Method of preparing a silylphosphate mixture, silylphosphate mixture and its use in stabilizing metal silanolates in siloxane polymers |
DE69112782T DE69112782T2 (en) | 1990-11-29 | 1991-05-14 | Process for the preparation of a silyl phosphate mixture, silyl phosphate mixture and their use for the stabilization of metal silanolates in siloxane polymers. |
JP03158232A JP3083591B2 (en) | 1990-11-29 | 1991-06-28 | Silyl phosphate mixture, process for its preparation and use for stabilizing metal silanolates in siloxane polymers |
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US07/622,051 US5041586A (en) | 1990-11-29 | 1990-11-29 | Method of preparing a silyphosphate mixture, silyphosphate mixture and its use in stabilizing metal silanolates in siloxane polymers |
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US5041586A true US5041586A (en) | 1991-08-20 |
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US07/622,051 Expired - Lifetime US5041586A (en) | 1990-11-29 | 1990-11-29 | Method of preparing a silyphosphate mixture, silyphosphate mixture and its use in stabilizing metal silanolates in siloxane polymers |
Country Status (4)
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US (1) | US5041586A (en) |
EP (1) | EP0488490B1 (en) |
JP (1) | JP3083591B2 (en) |
DE (1) | DE69112782T2 (en) |
Cited By (15)
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US5099051A (en) * | 1991-08-16 | 1992-03-24 | Dow Corning Corporation | Siloxanyl-phosphate mixture and its use in stabilizing metal silanolates in siloxane polymers |
US5481015A (en) * | 1994-01-27 | 1996-01-02 | Dow Corning Toray Silicone Co., Ltd. | Method for preparation of siloxanyl phosphate |
US5481014A (en) * | 1995-05-08 | 1996-01-02 | Dow Corning Corporation | Silyl phosphonate as stabilizing agent for polydiorganosiloxanes |
US5492995A (en) * | 1994-02-11 | 1996-02-20 | Hoechst Aktiengsellschaft | Polycondensates containing phosphinic or phosphonic acid groups and siloxane groups |
US5710300A (en) * | 1997-04-11 | 1998-01-20 | Dow Corning Corporation | Siloxy phosphonate as stabilizing agent for polydiorganosiloxanes |
US5922816A (en) * | 1992-06-02 | 1999-07-13 | General Electric Company | Polyester-polycarbonate compositions stabilized against ester-carbonate interchange |
US6013217A (en) * | 1997-12-22 | 2000-01-11 | Dow Corning Corporation | Method for extruding thermoplastic resins |
EP1580215A1 (en) * | 2004-03-23 | 2005-09-28 | Wacker-Chemie GmbH | Process for the preparation of aminofunctional organopolysiloxanes |
WO2007067332A2 (en) | 2005-12-08 | 2007-06-14 | Dow Corning Corporation | Continuous process for production of silicone pressure sensitive adhesives |
KR101009460B1 (en) * | 2009-02-05 | 2011-01-19 | 리켐주식회사 | Manufacturing process of high-purity Tristrimethylsilyl phosphate |
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JP2004217850A (en) * | 2003-01-17 | 2004-08-05 | Dow Corning Toray Silicone Co Ltd | Organopolysiloxane composition and curable organopolysiloxane composition |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3019248A (en) * | 1958-12-23 | 1962-01-30 | Union Carbide Corp | Process for making phosphorus-containing organosilicon compounds |
US3385822A (en) * | 1967-07-03 | 1968-05-28 | Gen Electric | Moisture curable polysiloxane phosphate composition |
US4125551A (en) * | 1978-02-13 | 1978-11-14 | General Electric Company | Process for producing silylphosphates |
US4177200A (en) * | 1977-11-25 | 1979-12-04 | General Electric Company | Silyl phosphates as neutralizing agents for alkali metal hydroxides |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1217335A (en) * | 1967-04-10 | 1970-12-31 | Midland Silicones Ltd | Polymerisation of siloxanes |
-
1990
- 1990-11-29 US US07/622,051 patent/US5041586A/en not_active Expired - Lifetime
-
1991
- 1991-05-14 DE DE69112782T patent/DE69112782T2/en not_active Expired - Lifetime
- 1991-05-14 EP EP91304296A patent/EP0488490B1/en not_active Expired - Lifetime
- 1991-06-28 JP JP03158232A patent/JP3083591B2/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3019248A (en) * | 1958-12-23 | 1962-01-30 | Union Carbide Corp | Process for making phosphorus-containing organosilicon compounds |
US3385822A (en) * | 1967-07-03 | 1968-05-28 | Gen Electric | Moisture curable polysiloxane phosphate composition |
US4177200A (en) * | 1977-11-25 | 1979-12-04 | General Electric Company | Silyl phosphates as neutralizing agents for alkali metal hydroxides |
US4125551A (en) * | 1978-02-13 | 1978-11-14 | General Electric Company | Process for producing silylphosphates |
Cited By (21)
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US5099051A (en) * | 1991-08-16 | 1992-03-24 | Dow Corning Corporation | Siloxanyl-phosphate mixture and its use in stabilizing metal silanolates in siloxane polymers |
EP0528508A1 (en) * | 1991-08-16 | 1993-02-24 | Dow Corning Corporation | Siloxanyl-phosphate mixture and its use in stabilizing metal silanolates in siloxane polymers |
US5922816A (en) * | 1992-06-02 | 1999-07-13 | General Electric Company | Polyester-polycarbonate compositions stabilized against ester-carbonate interchange |
US5481015A (en) * | 1994-01-27 | 1996-01-02 | Dow Corning Toray Silicone Co., Ltd. | Method for preparation of siloxanyl phosphate |
US5492995A (en) * | 1994-02-11 | 1996-02-20 | Hoechst Aktiengsellschaft | Polycondensates containing phosphinic or phosphonic acid groups and siloxane groups |
US5481014A (en) * | 1995-05-08 | 1996-01-02 | Dow Corning Corporation | Silyl phosphonate as stabilizing agent for polydiorganosiloxanes |
US5710300A (en) * | 1997-04-11 | 1998-01-20 | Dow Corning Corporation | Siloxy phosphonate as stabilizing agent for polydiorganosiloxanes |
US6013217A (en) * | 1997-12-22 | 2000-01-11 | Dow Corning Corporation | Method for extruding thermoplastic resins |
US7129369B2 (en) | 2004-03-23 | 2006-10-31 | Wacker Chemie Ag | Preparation of amino-functional organopolysiloxanes |
US20050215806A1 (en) * | 2004-03-23 | 2005-09-29 | Wacker-Chemie Gmbh | Preparation of amino-functional organopolysiloxanes |
EP1580215A1 (en) * | 2004-03-23 | 2005-09-28 | Wacker-Chemie GmbH | Process for the preparation of aminofunctional organopolysiloxanes |
WO2007067332A2 (en) | 2005-12-08 | 2007-06-14 | Dow Corning Corporation | Continuous process for production of silicone pressure sensitive adhesives |
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KR101249361B1 (en) * | 2010-12-16 | 2013-04-03 | 리켐주식회사 | Manufacturing process of high-purity Tris(trialkylsilyl)Phosphite |
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CN103408587A (en) * | 2013-08-30 | 2013-11-27 | 湖北兴发化工集团股份有限公司 | Preparation method of silica-based phosphate ester |
CN103408587B (en) * | 2013-08-30 | 2016-04-20 | 湖北兴发化工集团股份有限公司 | A kind of preparation method of silica-based phosphoric acid ester |
US9868902B2 (en) | 2014-07-17 | 2018-01-16 | Soulbrain Co., Ltd. | Composition for etching |
US10465112B2 (en) | 2014-07-17 | 2019-11-05 | Soulbrain Co., Ltd. | Composition for etching |
WO2016118472A1 (en) | 2015-01-20 | 2016-07-28 | Dow Corning Corporation | Silicone pressure sensitive adhesives |
US10351742B2 (en) | 2015-01-20 | 2019-07-16 | Dow Silicones Corporation | Silicone pressure sensitive adhesives |
Also Published As
Publication number | Publication date |
---|---|
EP0488490A1 (en) | 1992-06-03 |
JPH04334391A (en) | 1992-11-20 |
DE69112782T2 (en) | 1996-05-02 |
EP0488490B1 (en) | 1995-09-06 |
JP3083591B2 (en) | 2000-09-04 |
DE69112782D1 (en) | 1995-10-12 |
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